HAL Id: hal-02318101 https://hal.archives-ouvertes.fr/hal-02318101 Submitted on 8 Sep 2020 HAL is a multi-disciplinary open access archive for the deposit and dissemination of sci- entific research documents, whether they are pub- lished or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés. Using polymorphism to master the spin crossover mechanism in [Fe(PM-PeA)2(NCSe)2] Élodie Tailleur, Mathieu Marchivie, Philippe Négrier, Dominique Denux, Stéphane Massip, Denise Mondieig, Guillaume Chastanet, Philippe Guionneau To cite this version: Élodie Tailleur, Mathieu Marchivie, Philippe Négrier, Dominique Denux, Stéphane Massip, et al.. Using polymorphism to master the spin crossover mechanism in [Fe(PM-PeA)2(NCSe)2]. Crys- tEngComm, Royal Society of Chemistry, 2019, 21 (41), pp.6246-6251. 10.1039/C9CE01137D. hal- 02318101
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HAL Id: hal-02318101https://hal.archives-ouvertes.fr/hal-02318101
Submitted on 8 Sep 2020
HAL is a multi-disciplinary open accessarchive for the deposit and dissemination of sci-entific research documents, whether they are pub-lished or not. The documents may come fromteaching and research institutions in France orabroad, or from public or private research centers.
L’archive ouverte pluridisciplinaire HAL, estdestinée au dépôt et à la diffusion de documentsscientifiques de niveau recherche, publiés ou non,émanant des établissements d’enseignement et derecherche français ou étrangers, des laboratoirespublics ou privés.
Using polymorphism to master the spin crossovermechanism in [Fe(PM-PeA)2(NCSe)2]
Élodie Tailleur, Mathieu Marchivie, Philippe Négrier, Dominique Denux,Stéphane Massip, Denise Mondieig, Guillaume Chastanet, Philippe Guionneau
To cite this version:Élodie Tailleur, Mathieu Marchivie, Philippe Négrier, Dominique Denux, Stéphane Massip, et al..Using polymorphism to master the spin crossover mechanism in [Fe(PM-PeA)2(NCSe)2]. Crys-tEngComm, Royal Society of Chemistry, 2019, 21 (41), pp.6246-6251. �10.1039/C9CE01137D�. �hal-02318101�
Polymorphism to master the spin crossover mechanism
in [Fe(PM-PeA)2(NCSe)2]
Elodie TAILLEURa, Mathieu MARCHIVIEa, Philippe NEGRIERb, Dominique DENUXa, Stéphane
MASSIPc, Denise MONDIEIGb, Guillaume CHASTANETa, Philippe GUIONNEAU*a
In the crystalline state, a given molecule can lead to very different physical properties depending on the molecular packing
within the sample. Despite the spin crossover is by essence a molecular scale phenomenon, polymorphism lead to a large
diversity of the spin-switch features. The comparison of the structural and physical properties of spin crossover polymorphs
can therefore give crucial information about the phenomenon itself. As revealed by this study, the investigated molecular
iron(II) complex can be crystallized into two polymorphs, one showing a first order spin crossover with a large hysteresis
centered at room temperature and the other one showing a fully reversible gradual spin crossover at lower temperature.
The distinction between the two polymorphs is subtle and lies in the molecular stacking with regard to the interatomic
contacts of the H...H type, which underlines the extreme sensitivity of this physical phenomenon to the crystalline stacking.
Interestingly, the purposeful crystallization of these polymorphs opens up perspectives since it allows to choose dissimilar
spin crossover mechanisms starting from the same molecule.
Introduction
In the investigation of the Spin crossover (SCO) phenomenon,
polymorphism represents an exciting opportunity to
understand the complex relationships between the structural
properties and the switching features in the solid-state.1-3 Note
that despite solvatomorphism is also an interesting route4,
polymorphism seems more suitable for orienting towards a
choice of the SCO properties of a given compound, since for the
first one, the possibility of a solvent departure greatly
complicates the process. Hereafter, we are thus discussing
about solvent-free polymorphism. The SCO originates on the
metallic site, here iron(II). However, the SCO features are
affected by all the physical scales of the solid, from the atom up
to the crystal.5 The structure-property relationships in SCO
materials start to be well documented and the main learning of
the literature on this subject is the complexity of corresponding
close and subtle links. In this context, having different crystal
packing for identical molecular complexes, i. e. polymorphs,
makes it possible, for example, to track the structural origin of
some physical behavior, such as magnetic properties, by
meticulously comparing polymorphs' features.1-3, 6-9 This paper
provides a cornerstone to this building by probing two well-
crystallized polymorphs with radically different magnetic
properties - one with hysteresis at room temperature and the
other one with a continuous conversion occurring at low
temperature - using the crystal structures determined both at
high temperature when the iron is High-Spin (HS) and at low
temperature when the iron is Low-Spin (LS).
Crystals of the molecular complex [Fe(PM-PeA)2(NCSe)2] [with
PM PeA = N-(2’-pyridylmethylene)-4-(phenylethynyl) aniline)]
have been reported as being among the very rare - almost the
unique so far - to undergo a thermal-induced SCO centered at
room temperature (286 K) with a large hysteresis width (41 K).10
In that case, the SCO is accompanied by a peculiar structural
transition from mP21/c (HS) to oPccn (LS) that was also recently
observed with high-pressure acting as a stimulus.11 The already
reported polymorph will be hereafter named polymorph-I since
another polymorph, therefore named polymorph-II, has been
crystallized and constitutes the main purpose of this paper. The
objective, here, is to highlight the structural origin of the SCO
features differences shown by the two polymorphs. First, the
structural, magnetic and thermodynamics properties of
polymorph-II are reported then the comparison of selected
features of the two known polymorphs allows some progresses
on the knowledge of structure-property relationships in SCO
crystals.
Results and Discussions
a CNRS, Univ. Bordeaux, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France b Univ. Bordeaux, LOMA, UMR 5798, 33400 Talence, France c CNRS, IECB, UMS 3033, 33600 Pessac, France; Univ. Bordeaux, IECB, UMS 3033/US 001, Pessac, France Electronic Supplementary Information (ESI) available: X-ray patterns for different batches, temperature dependence of all unit-cell parameters, elementary analyses, full data collection strategies for single-crystal X-ray data. Cif files are deposited at the CSD with numbers 1937630 (293 K) and 1937632 (100 K). See DOI: 10.1039/x0xx00000x
‡ The unit-cell of polymorph I is mP21/c at 300 K in HS with a = 15.7175 (13) Å, b = 14.6860 (13) Å, c = 16.9957 (13) Å, β = 93,399 (3) and V= 3916.2 (6) Å3 and oPccn at 230 K in LS with a = 14.444 (5) Å, b = 14.705 (4) Å, c = 17.595 (4) Å and V= 3737.2 (17) Å3. 1 J. Tao, R.-J. Wei, R.-B. Huang and L.-S. Zheng, Chem. Soc. Rev.,
2012, 41, 703–737. 2 T.M. Ross, B. Moubaraki, S.M. Neville, S.R. Batten and K.S.
Murray, Dalton Trans., 2012, 41, 1512. 3 C. Bartual-Murgui, L. Pineiro-Lopez, F.J. Valverde-Munoz, M.
Carmen Munoz, M. Seredyuk and J.A. Real, Inorg. Chem., 2017, 56, 13535−13546.
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